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  Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method

Neese, F., Wennmohs, F., & Hansen, A. (2009). Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method. The Journal of Chemical Physics, 130(11): 114108. doi:10.1063/1.3086717.

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Neese, Frank1, 2, Author           
Wennmohs, Frank1, Author           
Hansen, Andreas1, Author
1Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              
2Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023879              


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 Abstract: Coupled-electron pair approximations (CEPAs) and coupled-pair functionals (CPFs) have been popular in the 1970s and 1980s and have yielded excellent results for small molecules. Recently, interest in CEPA and CPF methods has been renewed. It has been shown that these methods lead to competitive thermochemical, kinetic, and structural predictions. They greatly surpass second order Møller–Plesset and popular density functional theory based approaches in accuracy and are intermediate in quality between CCSD and CCSD(T) in extended benchmark studies. In this work an efficient production level implementation of the closed shell CEPA and CPF methods is reported that can be applied to medium sized molecules in the range of 50–100 atoms and up to about 2000 basis functions. The internal space is spanned by localized internal orbitals. The external space is greatly compressed through the method of pair natural orbitals (PNOs) that was also introduced by the pioneers of the CEPA approaches. Our implementation also makes extended use of density fitting (or resolution of the identity) techniques in order to speed up the laborious integral transformations. The method is called local pair natural orbital CEPA (LPNO-CEPA) (LPNO-CPF). The implementation is centered around the concepts of electron pairs and matrix operations. Altogether three cutoff parameters are introduced that control the size of the significant pair list, the average number of PNOs per electron pair, and the number of contributing basis functions per PNO. With the conservatively chosen default values of these thresholds, the method recovers about 99.8% of the canonical correlation energy. This translates to absolute deviations from the canonical result of only a few kcal mol−1. Extended numerical test calculations demonstrate that LPNO-CEPA (LPNO-CPF) has essentially the same accuracy as parent CEPA (CPF) methods for thermochemistry, kinetics, weak interactions, and potential energy surfaces but is up to 500 times faster. The method performs best in conjunction with large and flexible basis sets. These results open the way for large-scale chemical applications.


Language(s): eng - English
 Dates: 2008-11-262009-03-202009-03-21
 Publication Status: Published in print
 Pages: 18
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/1.3086717
 Degree: -



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Title: The Journal of Chemical Physics
  Abbreviation : J. Chem. Phys.
Source Genre: Journal
Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 130 (11) Sequence Number: 114108 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226